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The fabrication of heterostructures of two-dimensional semiconductors with specific bandgaps is an important approach to realizing the full potential of these materials in electronic and optoelectronic devices. Several groups have recently reported the direct growth of lateral and vertical heterostructures based on monolayers of typical semiconducting transition metal dichalcogenides (TMDCs) such as WSe2, MoSe2, WS2, and MoS2. Here, we demonstrate the single-step direct growth of lateral and vertical heterostructures based on bandgap-tunable Mo1-xWxS2 alloy monolayers by the sulfurization of patterned thin films of WO3 and MoO3. These patterned films are capable of generating a wide variety of concentration gradients by the diffusion of transition metals during the crystal growth phase. Under high temperatures, this leads to the formation of monolayer crystals of Mo1-xWxS2 alloys with various compositions and bandgaps, depending on the positions of the crystals on the substrates. Heterostructures of these alloys are obtained through stepwise changes in the ratio of W/Mo within a single domain during low-temperature growth. The stabilization of the monolayer Mo1-xWxS2 alloys, which often degrade even under gentle conditions, was accomplished by coating the alloys with other monolayers. The present findings demonstrate an efficient means of both studying and optimizing the optical and electrical properties of TMDC-based heterostructures to allow use of the materials in future device applications.


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Bandgap-tunable lateral and vertical heterostructures based on monolayer Mo1-xWxS2 alloys

Show Author's information Yu Kobayashi1Shohei Mori1Yutaka Maniwa1Yasumitsu Miyata1,2( )
Department of Physics Tokyo Metropolitan UniversityHachioji, Tokyo 192-0397 Japan
JST PRESTOKawaguchi Saitama 332-0012Japan

Abstract

The fabrication of heterostructures of two-dimensional semiconductors with specific bandgaps is an important approach to realizing the full potential of these materials in electronic and optoelectronic devices. Several groups have recently reported the direct growth of lateral and vertical heterostructures based on monolayers of typical semiconducting transition metal dichalcogenides (TMDCs) such as WSe2, MoSe2, WS2, and MoS2. Here, we demonstrate the single-step direct growth of lateral and vertical heterostructures based on bandgap-tunable Mo1-xWxS2 alloy monolayers by the sulfurization of patterned thin films of WO3 and MoO3. These patterned films are capable of generating a wide variety of concentration gradients by the diffusion of transition metals during the crystal growth phase. Under high temperatures, this leads to the formation of monolayer crystals of Mo1-xWxS2 alloys with various compositions and bandgaps, depending on the positions of the crystals on the substrates. Heterostructures of these alloys are obtained through stepwise changes in the ratio of W/Mo within a single domain during low-temperature growth. The stabilization of the monolayer Mo1-xWxS2 alloys, which often degrade even under gentle conditions, was accomplished by coating the alloys with other monolayers. The present findings demonstrate an efficient means of both studying and optimizing the optical and electrical properties of TMDC-based heterostructures to allow use of the materials in future device applications.

Keywords: stability, heterostructure, photoluminescence, alloy, transition metal dichalcogenide, Mo1–xWxS2, thin-film sulfurization

References(38)

1

Geim, A. K.; Grigorieva, I. V. Van der Waals heterostructures. Nature 2013, 499, 419-425.

2

Dean, C. R.; Young, A. F.; Meric, I; Lee, C.; Wang, L.; Sorgenfrei, S.; Watanabe, K.; Taniguchi, T.; Kim, P.; Shepard, K. L. et al. Boron nitride substrates for high-quality graphene electronics. Nat. Nanotechnol. 2010, 5, 722-726.

3

Dean, C.; Young, A. F.; Wang, L.; Meric, I.; Lee, G. -H.; Watanabe, K.; Taniguchi, T.; Shepard, K.; Kim, P.; Hone, J. Graphene based heterostructures. Solid State Commun. 2012, 152, 1275-1282.

4

Georgiou, T.; Jalil, R.; Belle, B. D.; Britnell, L.; Gorbachev, R. V.; Morozov, S. V.; Kim, Y. -J.; Gholinia, A.; Haigh, S. J.; Makarovsky, O. et al. Vertical field-effect transistor based on graphene-WS2 heterostructures for flexible and transparent electronics. Nat. Nanotechnol. 2013, 8, 100-103.

5

Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.; Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotechnol. 2012, 7, 699-712.

6

Lee, G. -H.; Yu, Y. -J.; Cui, X.; Petrone, N.; Lee, C. -H.; Choi, M. S.; Lee, D. -Y.; Lee, C.; Yoo, W. J.; Watanabe, K. et al. Flexible and transparent MoS2 field-effect transistors on hexagonal boron nitride-graphene heterostructures. ACS Nano 2013, 7, 7931-7936.

7

Wang, L.; Meric, I.; Huang, P. Y.; Gao, Q.; Gao, Y.; Tran, H.; Taniguchi, T.; Watanabe, K.; Campos, L. M.; Muller, D. A. et al. One-dimensional electrical contact to a two-dimensional material. Science 2013, 342, 614-617.

8

Gorbachev, R. V.; Song, J. C. W.; Yu, G. L.; Kretinin, A. V.; Withers, F.; Cao, Y.; Mishchenko, A.; Grigorieva, I. V.; Novoselov, K. S.; Levitov, L. S. et al. Detecting topological currents in graphene superlattices. Science 2014, 346, 448-451.

9

Roy, K.; Padmanabhan, M.; Goswami, S.; Sai, T. P.; Ramalingam, G.; Raghavan, S.; Ghosh, A. Graphene-MoS2 hybrid structures for multifunctional photoresponsive memory devices. Nat. Nanotechnol. 2013, 8, 826-830.

10

Hunt, B.; Sanchez-Yamagishi, J. D.; Young, A. F.; Yankowitz, M.; LeRoy, B. J.; Watanabe, K.; Taniguchi, T.; Moon, P.; Koshino, M.; Jarillo-Herrero, P. et al. Massive dirac fermions and hofstadter butterfly in a van der Waals heterostructure. Science 2013, 340, 1427-1430.

11

Yu, Y. F.; Hu, S.; Su, L. Q.; Huang, L. J.; Liu, Y.; Jin, Z. H.; Purezky, A. A.; Geohegan, D. B.; Kim, K. W.; Zhang, Y. et al. Equally efficient interlayer exciton relaxation and improved absorption in epitaxial and nonepitaxial MoS2/WS2 heterostructures. Nano Lett. 2015, 15, 486-491.

12

Levendorf, M. P.; Kim, C. -J.; Brown, L.; Huang, P. Y.; Havener, R. W.; Muller, D. A.; Park, J. Graphene and boron nitride lateral heterostructures for atomically thin circuitry. Nature 2012, 488, 627-632.

13

Sutter, P.; Cortes, R.; Lahiri, J.; Sutter, E. Interface formation in monolayer graphene-boron nitride heterostructures. Nano Lett. 2012, 12, 4869-4874.

14

Miyata, Y.; Maeda, E.; Kamon, K.; Kitaura, R.; Sasaki, Y.; Suzuki, S.; Shinohara, H. Fabrication and characterization of graphene/hexagonal boron nitride hybrid sheets. Appl. Phys. Express 2012, 5, 085102.

15

Liu, Z.; Ma, L. L.; Shi, G.; Zhou, W.; Gong, Y. J.; Lei, S. D.; Yang, X. B.; Zhang, J. N.; Yu, J. J.; Hackenberg, K. P. et al. In-plane heterostructures of graphene and hexagonal boron nitride with controlled domain sizes. Nat. Nanotechnol. 2013, 8, 119-124.

16

Liu, L.; Park, J.; Siegel, D. A.; McCarty, K. F.; Clark, K. W.; Deng, W.; Basile, L.; Idrobo, J. C.; Li, A. -P.; Gu, G. Heteroepitaxial growth of two-dimensional hexagonal boron nitride templated by graphene edges. Science 2014, 343, 163-167.

17

Han, G. H.; Rodríguez-Manzo, J. A.; Lee, C. -W.; Kybert, N. J.; Lerner, M. B.; Qi, Z. J.; Dattoli, E. N.; Rappe, A. M.; Drndic, M.; Johnson, A. T. C. Continuous growth of hexagonal graphene and boron nitride in-plane heterostructures by atmospheric pressure chemical vapor deposition. ACS Nano 2013, 7, 10129-10138.

18

Havener, R. W.; Kim, C. -J.; Brown, L.; Kevek, J. W.; Sleppy, J. D.; McEuen, P. L.; Park, J. Hyperspectral imaging of structure and composition in atomically thin heterostructures. Nano Lett. 2013, 13, 3942-3946.

19

Gao, Y. B.; Zhang, Y. F.; Chen, P. C.; Li, Y. C.; Liu, M. X.; Gao, T.; Ma, D. L.; Chen, Y. B.; Cheng, Z. H.; Qiu, X. H. et al. Toward single-layer uniform hexagonal boron nitride-graphene patchworks with zigzag linking edges. Nano Lett. 2013, 13, 3439-3443.

20

Gong, Y. J.; Lin, J. H.; Wang, X. L.; Shi, G.; Lei, S. D.; Lin, Z.; Zou, X. L.; Ye, G. L.; Vajtai, R.; Yakobson, B. I. et al. Vertical and in-plane heterostructures from WS2/MoS2 monolayers. Nat. Mater. 2014, 13, 1135-1142.

21

Duan, X. D.; Wang, C.; Shaw, J. C.; Cheng, R.; Chen, Y.; Li, H. L.; Wu, X. P.; Tang, Y.; Zhang, Q. L.; Pan, A. L. et al. Lateral epitaxial growth of two-dimensional layered semiconductor heterojunctions. Nat. Nanotechnol. 2014, 9, 1024-1030.

22

Huang, C. M.; Wu, S. F.; Sanchez, A. M.; Peters, J. J. P.; Beanland, R.; Ross, J. S.; Rivera, P.; Yao, W.; Cobden, D. H.; Xu, X. D. Lateral heterojunctions within monolayer MoSe2/ WSe2 semiconductors. Nat. Mater. 2014, 13, 1096-1101.

23

Zhang, X. -Q.; Lin, C. -H.; Tseng, Y. -W.; Huang, K. -H.; Lee, Y. -H. Synthesis of lateral heterostructures of semiconducting atomic layers. Nano Lett. 2015, 15, 410-415.

24

Chen, Y. F.; Xi, J. Y.; Dumcenco, D. O.; Liu, Z.; Suenaga, K.; Wang, D.; Shuai, Z. G.; Huang, Y. -S.; Xie, L. M. Tunable band gap photoluminescence from atomically thin transition-metal dichalcogenide alloys. ACS Nano 2013, 7, 4610-4616.

25

Gong, Y. J.; Liu, Z.; Lupini, A. R.; Shi, G.; Lin, J. H.; Najmaei, S.; Lin, Z.; Elías, A. L.; Berkdemir, A.; You, G. et al. Band gap engineering and layer-by-layer mapping of selenium-doped molybdenum disulfide. Nano Lett. 2014, 14, 442-449.

26

Chen, Y. F.; Dumcenco, D. O.; Zhu, Y. M.; Zhang, X.; Mao, N. N.; Feng, Q. L.; Zhang, M.; Zhang, J.; Tan, P. -H.; Huang, Y. -S. et al. Composition-dependent raman modes of Mo1-xWxS2 monolayer alloys. Nanoscale 2013, 6, 2833-2839.

27

Zhao, W. J.; Ghorannevis, Z.; Chu, L. Q.; Toh, M. L.; Kloc, C.; Tan, P. -H.; Eda, G. Evolution of electronic structure in atomically thin sheets of WS2 and WSe2. ACS Nano 2013, 7, 791-797.

28

Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Atomically thin MoS2: A new direct-gap semiconductor. Phys. Rev. Lett. 2010, 105, 136805.

29

Splendiani, A.; Sun, L.; Zhang, Y. B.; Li, T. S.; Kim, J.; Chim, C. -Y.; Galli, G.; Wang, F. Emerging photoluminescence in monolayer MoS2. Nano Lett. 2010, 10, 1271-1275.

30

Zhou, H. Q.; Yu, F.; Liu, Y. Y.; Zou, X. L.; Cong, C. X.; Qiu, C. Y.; Yu, T.; Yan, Z.; Shen, X. N.; Sun, L. F. et al. Thickness-dependent patterning of MoS2 sheets with well-oriented triangular pits by heating in air. Nano Res. 2013, 6, 703-711.

31

Tongay, S.; Suh, J.; Ataca, C.; Fan, W.; Luce, A.; Kang, J. S.; Liu, J.; Ko, C.; Raghunathanan, R.; Zhou, J. et al. Defects activated photoluminescence in two-dimensional semiconductors: Interplay between bound, charged, and free excitons. Sci. Rep. 2013, 3, 2657.

32

Bissett, M. A.; Konabe, S.; Okada, S.; Tsuji, M.; Ago, H. Enhanced chemical reactivity of graphene induced by mechanical strain. ACS Nano 2013, 7, 10335-10343.

33

Kobayashi, Y.; Sasaki, S.; Mori, S.; Hibino, H.; Liu, Z.; Watanabe, K.; Taniguchi, T.; Suenaga, K.; Maniwa, Y.; Miyata, Y. Growth and optical properties of high-quality monolayer WS2 on graphite. ACS Nano 2015, 9, 4056-4063.

34

Orofeo, C. M.; Suzuki, S.; Sekine, Y.; Hibino, H. Scalable synthesis of layer-controlled WS2 and MoS2 sheets by sulfurization of thin metal films. Appl. Phys. Lett. 2014, 105, 083112.

35

Gutiérrez, H. R.; Perea-López, N.; Elías, A. L.; Berkdemir, A.; Wang, B.; Lv, R. T.; López-Urías, F.; Crespi, V. H.; Terrones, H.; Terrones, M. Extraordinary room-temperature photoluminescence in triangular WS2 monolayers. Nano Lett. 2013, 13, 3447-3454.

36

Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. -J.; Loh, K. P.; Zhang, H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263-275.

37

Yu, Q. K.; Jauregui, L. A.; Wu, W.; Colby, R.; Tian, J. F.; Su, Z. H.; Cao, H. L.; Liu, Z. H.; Pandey, D.; Wei, D. G. et al. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nat. Mater. 2011, 10, 443-449.

38

Ren, Y. J.; Zhu, C. F.; Cai, W. W.; Li, H. F.; Hao, Y. F.; Wu, Y. P.; Chen, S. S.; Wu, Q. Z.; Piner, R. D.; Ruoff, R. S. An improved method for transferring ggarphene grown by chemical vapor deposition. Nano 2012, 7, 1150001.

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Publication history
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Acknowledgements

Publication history

Received: 10 March 2015
Revised: 01 May 2015
Accepted: 30 May 2015
Published: 26 August 2015
Issue date: October 2015

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2015

Acknowledgements

Acknowledgements

This work was supported by a Grant-in-Aid for Young Scientist (A) (No. 15H05412) and for Scientific Research on Innovative Areas (No. 26107530) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, and by the Izumi Science and Technology Foundation.

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